1. Field of the Invention
This invention relates to polymeric materials which modify the rheological behavior of crosslinkable resin systems.
2. Introduction to the Invention
Crosslinkable resin systems are well known. It is known that in order to produce such a system which is relatively stable in storage, one of the active chemical moieties (e.g., a catalytic moiety or a reactive moiety) can be present in a xe2x80x9clatentxe2x80x9d form, which can be activated (by heating or otherwise) when rapid reaction is desired. Reference may be made for example to U.S. Pat. Nos. 4,349,651, 4,358,571, 4,420,605, 4,430,445, 4,659,779, 4,689,388, 4,701,378, 4,742,148 and 4,933,392 and European Patent Publication No. 362787A2. Copending, commonly assigned, U.S. application Ser. Nos. 08/726,739, 08/726,740 and 08/726,741 , all abandoned (each of which was filed Oct. 15, 1996 and claims priority from U.S. application Ser. No. 08/399,724 filed Mar. 7, 1995, now abandoned) and corresponding International Application No. PCT/US96/03023 (published Sep. 12, 1996, as International Publication No. WO-96/27641) disclose particularly valuable latent materials comprising an active chemical moiety which is bonded to a side chain crystalline (SCC) polymer moiety or to another crystalline polymeric moiety which melts over a narrow temperature range. These latent materials, which are referred to in the applications as polymeric modifying agents, are preferably in the form of particles having an average size of 0.1 to 50 microns. Copending, commonly assigned U.S. application Ser. No. 08/710,161 (Docket No. 10762-4 filed Sep. 12, 1996), abandoned, and corresponding International Application No. PCT/US 97/16019 (which was not published at the date of this application) disclose that even when there is no chemical bond between the active and polymeric moieties, a physical bond between the moieties can produce a lesser but still useful latent effect. Application Ser. Nos. 08/726,739, 08/726,740, 08/726,741 and 08/710,161 have all been abandoned in favor of a continuation-in-part application, Ser. No. 09/216,520, filed Dec. 16, 1998, U.S. Pat. No. 6,255,367. It is also known that curable resin systems tend to shrink when they cure, and that in some systems this tendency can be lessened or overcome by adding various polymeric additives; such additives are referred to as low profile additives (often abbreviated to xe2x80x9cLPAxe2x80x9ds). Reference may be made for example to pages 48 to 78 (Chapter 4 by Kenneth E. Atkins) in xe2x80x9cSheet Molding Compoundsxe2x80x9d, edited by Hamid Kia (1993), Plastics Compounding, July/August 1988, pages 35-45, and U.S. Pat. Nos. 3,674,893, 3,718,714, 3,721,642, 3,772,241, 3,842,142, 4,125,702, 4,160,759, 4,161,471, 4,245,068, 4,284,736, 4,288,571, 4,374,215, 4,491,642, 4,555,534, 4,673,706, 5,290,854, 5,428,105, 5,504,151, 5,552,478 and 5,589,538.
The disclosure of each of the U.S. patents and patent applications, International and European patent publications, and literature references referred to in the preceding paragraph is incorporated herein by reference for all purposes.
We have discovered, in accordance with the present invention, that the rheological properties of a crosslinkable resin system can be substantially improved by the presence of an SCC polymer (or a similar crystalline polymer which melts over a narrow temperature range). The polymer must be one which (a) at least partially dissolves in the curable system at temperatures above the melting point of the crystalline polymer (Tp) and (b) when the curable composition is (i) heated to a temperature above Tp under conditions such that the resin does not cure and (ii) is then cooled to a temperature below Tp, at least partially forms a separate phase in the curable system. At temperatures below Tp, the presence of this separate phase substantially increases the viscosity of the curable system (i.e. makes it thicker than the same system without the crystalline polymer). This is particularly valuable for sheet molding composites (SMCs), in which the increase in viscosity makes the composites less tacky and, therefore, (a) easier to handle cleanly, and (b) more likely to yield a cured product having a surface free from flaws. Above Tp, the curable system containing the dissolved crystalline polymer has a viscosity which is substantially less than its viscosity below Tp.
The crystalline polymer can be, but need not be, chemically or physically bound to an active chemical moiety which will take part in the reaction which forms the cured polymer. We believe, therefore, that under appropriate circumstances, some latent materials of the kind described in the copending, commonly assigned U.S. patent applications referred to above will function as RHMs. However, that possibility is not disclosed in those U.S. patent applications or the corresponding PCT applications. Under these circumstances, the extent to which our discovery can be the subject of patent protection may vary from country to country. Accordingly, and since this specification will serve not only as the specification for this U.S. patent application, but also as the priority document for corresponding applications elsewhere, the present invention is broadly defined as any product or process which embodies our discovery and which can properly be the subject of patent protection.
In a first preferred aspect, this invention provides a polymeric composition which comprises
1. a matrix material which
(a) provides a continuous phase, and
(b) comprises precursors which will react together to form a crosslinked polymer;
and
2. a rheological modifier (RHM) which
(a) comprises a crystalline polymer having an onset of melting temperature To and a peak melting temperature Tp which is (i) from 20xc2x0 C. to 200xc2x0 C., and (ii) such that Tpxe2x88x92To is less than Tp0.7,
(b) is uniformly distributed in the matrix material,
(c) is at least partially soluble in the matrix material when the composition is subjected to a treatment which consists of maintaining the composition at a temperature above Tp under conditions such that the precursors do not react together to form a crosslinked resin, and
(d) becomes at least partially insoluble in the matrix material when the composition is subjected to said treatment at a temperature above Tp and is then cooled to a temperature below To,
the composition
(A) having a viscosity above Tp which is less than its viscosity below To; and
(B) having a viscosity at a temperature below To which is substantially greater than the viscosity at the same temperature of a composition which is identical except that it does not contain the rheological modifier.
Preferably, the matrix material and the RHM and the relative amounts thereof are such that (a) the composition, or (b) if the composition contains solid fillers, a composition which is identical except that it does not contain the solid fillers, (A) has a viscosity at (Tpxe2x88x9210)xc2x0 C. which is at least twice, preferably at least 5 times, its viscosity at (Tp+10)xc2x0 C.; and/or (B) has a viscosity at 20xc2x0 C. which is at least twice, preferably at least 5 times, the viscosity of a composition which is identical except that it does not contain the RHM.
The composition may also have at least one of the following characteristics, each of which provides an alternative or additional distinction over the disclosure of the commonly assigned U.S. applications and their PCT equivalents referred to above.
(1) At least 10%, at least 20% or at least 30% of the crystalline polymer is present in the form of particles or other discrete volumes which do not contain any material which takes part in the reaction which forms the crosslinked polymer.
(2) The composition, when maintained at 40xc2x0 C., doubles in viscosity in less than 240 hours, e.g. in less than 24 hours.
(3) The RHM is not present in the form of discrete particles.
(4) The RHM is added to the matrix material in the form of particles having an average size of at least 75 microns, or as a solution in a solvent.
(5) When the composition is heated from (Tpxe2x88x9210)xc2x0 C. to (Tp+10)xc2x0 C., there is an increase by a factor of less than 50, e.g., less than 5, in the effective concentration of each of the materials which takes part in the reaction which forms the crosslinked polymer.
It is to be understood that these characteristics (1) to (5) are not intended to represent factors which will be technically advantageous.
In a second preferred aspect, this invention provides a method of making such a composition which comprises
(A) dispersing the RHM, e.g. a solution of the RHM or particles of the RHM, in at least part of the matrix material;
(B) heating the product of step (A) to a temperature above Tp under conditions such that the precursors do not react together to form a crosslinked polymer; and
(C) cooling the heated dispersion to a temperature below Tp.
In a third preferred aspect, this invention provides a method of making a crosslinked polymer which comprises subjecting a composition as defined above to conditions which cause the precursor to react to form a crosslinked polymer.
In this specification, parts and percentages are by weight, viscosities are in centipoise and are measured using a Brookfield LVT viscometer, temperatures are in xc2x0 C., and To, Tp and heat of fusion are determined using a differential scanning calorimeter (DSC), (at a rate of temperature change of 10xc2x0 C./min on the second heat by cycle). To and Tp are measured in the conventional way well known to those skilled in the art. Thus Tp is the temperature at the peak of the DSC curve, and To is the temperature at the intersection of the baseline of the DSC peak and the onset line, the onset line being defined as the tangent to the steepest part of the DSC curve below Tp. The abbreviations Mw and Mn are used to denote weight average and number average molecular weight respectively. The abbreviation CxA is used to denote an n-alkyl acrylate in which the n-alkyl group contains x carbon atoms, the abbreviation Cx alkyl is used herein to denote an n-alkyl group which contains x carbon atoms, and the abbreviations CxM is used to denote an n-alkyl methacrylate in which the n-alkyl group contains x carbon atoms. Other abbreviations are given elsewhere in the specification.
The terms xe2x80x9cmatrixxe2x80x9d and xe2x80x9cmatrix materialsxe2x80x9d are used in this specification to denote any material or mixture of materials comprising a precursor which will react with itself to form a crosslinked polymer, or two or more precursors which will react with each other to form a crosslinked polymer, or one or more precursors which will react with one or more additional materials (added at a later stage) to form a crosslinked polymer. One or more of the precursors can be in latent form. The matrix generally comprises at least one solid or liquid material which provides a continuous phase in which the RHM is distributed. The matrix can include, in addition to the precursor(s) and the RHM, one or more other materials. Such materials can be compounds which influence the nature or the rate of the crosslinking reaction, and which can be in latent form, e.g. catalysts, polymerization inhibitors, and polymerization initiators. Such materials can also be added at a later stage, prior to the crosslinking reaction. Initiators may be present, for example, in amount 0.1 to 5%, and include organic derivatives of hydrogen peroxide such as para-t-butyl peroxybenzoate and 1,1-di-t-amyl peroxycyclohexane. Such other materials can also be, for example, materials which affect the physical properties of the curable resin or of the cured resin, for example fillers, LPAs, thickening agents, mold release agents, viscosity reducers, wetting agents and colorants. Such other materials can also be coadditives as disclosed in the pending U.S. applications referred to above. Suitable fillers include inorganic and organic materials, including fibrous fillers such as glass, Kevlar or carbon fibers, hollow glass microspheres, hollow polymeric microspheres, calcium carbonate and alumina trihydrate. The amount of filler, if present, may be 10 to 70%, for example 15 to 35%, and may be such that the curable composition has the consistency of a paste or is even a self-supporting solid. The amount of mold release agent, if present, may be 1 to 4%; mold release agents include calcium and zinc sterates. The amount of colorant, if present, may be 0.5 to 4%. The amount of thickener, if present, may be 0.1 to 3%; thickeners include magnesium oxide and calcium hydroxide.
The invention is particularly useful in the preparation of molded products of a cured resin derived from an unsaturated polyester (optionally with styrene), a vinyl ester, an acrylic resin, or an epoxy resin. The term xe2x80x9cunsaturated polyesterxe2x80x9d is used in this specification in its conventional sense to mean a polymer in which the monomer units are linked to each other through an ester group and which contains carbonxe2x80x94carbon double bonds that are capable of undergoing further polymerization. The term xe2x80x9cvinyl esterxe2x80x9d is likewise used in its conventional sense to denote a subclass of the unsaturated polyesters, namely those which contain vinyl groups, in particular polymers made by addition reactions involving polyepoxides and unsaturated acids. In order to prepare crosslinked thermoset resins from these polymers, they are generally dissolved in a monomer such as styrene and then copolymerized with the monomer. Other precursors include cyanate esters, isocyanurates, imides, bismaleimides, ureas, cyanoacrylates, epoxy novolac, resins, polyurethanes and phenolic resins.
The invention is particularly useful for reducing the tack at ambient temperatures of a curable resin composition which contains a relatively large amount of filler and/or other ingredient (e.g. 20 to 50% of glass fibers, or of hollow glass or polymeric microspheres), so that the composition has the consistency of a paste, or even is a self-supporting solid. Applications of this type include SMCs, particularly SMCs based on a mixture of an unsaturated polyester and styrene or another unsaturated comonomer. The invention is also useful for improving the moldability of curable compositions at temperatures above Tp. The RHM may also improve the release properties of the cured resin from a mold, and/or reduce the tendency of cured resin articles to stick to each other. Thus the invention is particularly useful in the preparation of dry film resists (DFRs) and flexographic print plates, as described for example in The Multilayer Printed Circuit Board, J A Scarlett (1985), and the Printed Circuit Handbook, Clyde F. Coombs (1988).
For further details of suitable precursors of the cured resin and other ingredients, reference should be made to the documents referred to above and incorporated herein by reference, and to
(a) Handbook of Epoxy Resins by Henry Lee and Kris Neville; 1967; McGraw-Hill Inc.
(b) Epoxy Resins, Chemistry and Technology 2nd Edition, edited by Clayton A. May; 1988; Marcel Dekker, Inc.
(c) Polyurethanes, Chemistry, Technology and Applications by Z. Wirpsza; 1993; Ellis Norwood Ltd.
(d) The ICI Polyurethanes Book by George Woods; 1987; John Wiley and Sons, Inc.
(e) Structural Adhesives, Chemistry and Technology, edited by S. R. Hartshort; 1986; Plenum Press
(f) Test Methods for Epoxy Compounds; published by the Society of the Plastics Industry, Inc., Epoxy Resin Formlations Division
(g) Thermal Characterization of Polymeric Materials, edited by Edith A. Turi; 1981; Academic Press, Inc., and
(h) Reaction Polymers, edited by Wilson F. Gum et al, Hanser Publishing.
The disclosure of each of documents (a) to (h) above is incorporated herein by reference.
The crystalline polymer in the RHM (the term xe2x80x9ccrystalline polymerxe2x80x9d being used to include a crystalline polymeric moiety which is chemically bound to a non-crystalline moiety) can be a single polymer or a mixture of polymers, and the polymer can be a homopolymer, or a copolymer of two or more comonomers, including random copolymers, graft copolymers, block copolymers and thermoplastic elastomers. Preferably at least part of the polymeric moiety is derived from a side chain crystallizable (SCC) polymer. The SCC polymer may for example be derived from one or more acrylic, methacrylic, olefinic, epoxy, vinyl, ester-containing, amide-containing or ether-containing monomers. The molecular weight of an SCC polymer is relatively unimportant to its Tp, but is generally an important factor in determining the Tp of other polymers. The preferred SCC polymeric moieties are described in detail below. However, the invention includes the use of other crystalline polymers having the desired properties. Such other polymers include for example polymers in which the crystallinity results exclusively or predominantly from the polymer backbone, e.g. polymers of a-olefins containing 2 to 12, preferably 2 to 8, carbon atoms, e.g. polymers of monomers having the formula CH2xe2x95x90CHR, where R is hydrogen, methyl, propyl, butyl, pentyl, 4-methylpentyl, hexyl or heptyl, as well as other polymers such as polyesters, polyamides, and polyalkylene oxides, for example polytetrahydrofuran.
It is important that the polymeric moiety should melt over a relatively small temeprature range. The closer Tp is to room temperature, the more rapid the transition should preferably be. Thus Tpxe2x88x92To is preferably less than Tp0.7, particularly less than Tp0.6, To and Tp being in xc2x0 C. Tp can vary widely, depending on the conditions under which the composition is to be stored, shaped and cured. Thus in general, Tp is preferably at least 25xc2x0 C., for example 25 to 120xc2x0 C., preferably 35 to 70xc2x0 C. Tpxe2x88x92To is preferably less than 10xc2x0 C., particularly less than 8xc2x0 C., more particularly less than 6xc2x0 C., especially less than 4xc2x0 C.
SCC polymers which can be used in this invention include known SCC polymers, e.g. polymers derived from one or more monomers such as substituted and unsubstituted acrylates, methacrylates, fluoroacrylates, vinyl esters, acrylamides, methacrylamides, maleimides, xcex1-olefins, p-alkyl styrenes, alkylvinyl ethers, alkylethylene oxides, alkyl phosphazenes and amino acids; polyisocyanates; polyurethanes; polysilanes; polysiloxanes; and polyethers; all of such polymers containing long chain crystallizable groups. Suitable SCC polymers are described for example in J. Poly. Sci. 60, 19 (1962), J. Poly. Sci, (Polymer Chemistry) 7, 3053 (1969), 9, 1835, 3349, 3351, 3367, 10, 1657, 3347, 18, 2197, 19, 1871, J. Poly. Sci, Poly-Physics Ed 18 2197 (1980), J. Poly. Sci, Macromol. Rev, 8, 117 (1974), Macromolecules 12, 94 (1979), 13, 12, 15, 18, 2141, 19, 611, JACS 75, 3326 (1953), 76; 6280, Polymer J 17, 991 (1985); and Poly. Sci USSR 21, 241 (1979) and in the commonly assigned U.S. patent applications referred to above and their PCT equivalents.
Preferred SCC polymers comprise side chains comprising linear polymethylene moieties containing 12 to 50, especially 14 to 22, carbon atoms, or linear perfluorinated or substantially perfluorinated polymethylene moieties containing 6 to 50 carbon atoms. Polymers containing such side chains can be prepared by polymerizing one or more corresponding linear aliphatic acrylates or methacrylates, or equivalent monomers such as acrylamides or methacrylamides. A number of such monomers are available commercially, either as individual monomers or as mixtures of identified monomers, for example C12A, C14A, C16A, C18A, C22A, a mixture of C18A, C20A and C22A, a mixture of C26A to C40A, fluorinated C8A (AE800 from American Hoechst) and a mixture of fluorinated C8A, C10A and C12A (AE12 from American Hoechst). The polymers can optionally also contain units derived from one or more other comonomers preferably selected from other alkyl, hydroxyalkyl and alkoxyalkyl acrylates, methacrylates (e.g. glycidyl methacrylate), acrylamides and methacrylamides; acrylic and methacrylic acids; acrylamide; methacrylamide; maleic anhydride; and comonomers containing amine groups. Such other co-monomers are generally present in total amount less than 50%, particularly less than 35%, especially less than 25%, e.g. 0 to 15%. They may be added to modify the melting point or other physical properties of the polymers, in particular so as to make the crystalline polymer more compatible with the precursor(s) and/or the crosslinked resin, and thus promote the desired RHM activity. For example, in one embodiment, the crystalline polymer comprises (a) units derived from a monomer containing an n-alkyl group containing 12 to 50 carbon atoms and (b) at least 10% of units derived from a second monomer; and the matrix material comprises at least 10% of the second monomer or of units which are part of a polymer and are derived from the second monomer; preferably the crystalline polymer contains 10 to 50% of units derived from the second monomer, and the matrix material contains 20 to 50% of the second monomer, e.g. styrene. In another embodiment, the crystalline polymer contains 10 to 50% of units derived from the second monomer, and the matrix material comprises a polymer containing 10 to 70%, based on the matrix material, of units derived from the second monomer; preferably the matrix material comprises precursors for an acrylate polymer and the second monomer is an alkyl acrylate or an alkyl methacrylate in which the alkyl group contains 1 to 4 carbon atoms.